EP0243101A2 - 6-Arylpyridinthiosemicarbazone mit Wirksamkeit als Insektizide - Google Patents

6-Arylpyridinthiosemicarbazone mit Wirksamkeit als Insektizide Download PDF

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Publication number
EP0243101A2
EP0243101A2 EP87303374A EP87303374A EP0243101A2 EP 0243101 A2 EP0243101 A2 EP 0243101A2 EP 87303374 A EP87303374 A EP 87303374A EP 87303374 A EP87303374 A EP 87303374A EP 0243101 A2 EP0243101 A2 EP 0243101A2
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Prior art keywords
compound
alkyl
insects
insecticidal
hydrogen
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French (fr)
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EP0243101A3 (de
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Dat Phat Le
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Rohm and Haas Co
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Rohm and Haas Co
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
    • C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
    • C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
    • C07D213/24—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with substituted hydrocarbon radicals attached to ring carbon atoms
    • C07D213/44—Radicals substituted by doubly-bound oxygen, sulfur, or nitrogen atoms, or by two such atoms singly-bound to the same carbon atom
    • C07D213/53—Nitrogen atoms
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/34—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the groups, e.g. biuret; Thio analogues thereof; Urea-aldehyde condensation products
    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N47/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid
    • A01N47/08—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom not being member of a ring and having no bond to a carbon or hydrogen atom, e.g. derivatives of carbonic acid the carbon atom having one or more single bonds to nitrogen atoms
    • A01N47/28—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N<
    • A01N47/38—Ureas or thioureas containing the groups >N—CO—N< or >N—CS—N< containing the group >N—CO—N< where at least one nitrogen atom is part of a heterocyclic ring; Thio analogues thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D405/00—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom
    • C07D405/02—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings
    • C07D405/04—Heterocyclic compounds containing both one or more hetero rings having oxygen atoms as the only ring hetero atoms, and one or more rings having nitrogen as the only ring hetero atom containing two hetero rings directly linked by a ring-member-to-ring-member bond

Definitions

  • This invention is concerned with certain 6-aryl-pyridine thiosemicarbazones which are useful as insecticides, compositions containing them and the use of the compounds and compositions as insecticides.
  • Compounds of the present invention are particularly suitable for controlling plant-destructive insects in crops of cultivated plants, ornamentals and forestry.
  • the 6-aryl-pyridine thiosemicarbazones of the present invention differ from known compounds primarily by their 6-position substituent on the pyridine ring.
  • Compounds of the present invention are also distinguished by their insecticidal activity and selectivity against lepidopteran larvae without unacceptably adverse impact on beneficial insects.
  • the compounds of the present invention exhibit anti-juvenile hormone activity.
  • the compounds of the present invention are consumed by larvae, said larvae undergo a premature lethal metamorphosis. This activity is believed to be unique to this class of compounds.
  • the present invention provides insecticidal compounds comprising thiosemicarbazones of the formula: where
  • the present invention also provides insecticidal compositions containing insecticidal compounds of the invention and agronomically acceptable diluent or carrier.
  • the invention also extends to the use of these compounds and compositions as insecticides.
  • halo should be understood as including chloro, fluoro, bromo and iodo.
  • alkyl by itself or as part of another substituent, unless otherwise stated, includes straight and branched chain groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl and isobutyl.
  • haloalkyl by itself or as part of another substituent is an alkyl group of the stated number of carbon atoms having one or more halo atoms bonded thereto such as chloromethyl, 1- or 2-bromoethyl; trifluoromethyl and the like.
  • Typical compounds within the scope of the present invention include, but are not limited to:
  • preferred compounds of the present invention include those thiosemicarbazones of Formula I where any one or combination of two or more of the substituents conform to the following definitions:
  • most preferred compounds of the present invention include those thiosemicarbazones of Formula I where, independently
  • Those 6-aryl-pyridine thiosemicarbazones of Formula I which possess acidic or basic functional groups may be further reacted to form novel salts with appropriate bases or acids. These salts also exhibit pesticidal activity.
  • Typical salts are the agronomically acceptable metal salts, ammonium salts and acid addition salts.
  • the metal salts are those in which the metal cation is an alkali metal cation such as sodium potassium or lithium; alkaline earth metal cation such as calcium, magnesium, barium or strontium; or heavy metal cation such as zinc, manganese, cupric, cuprous, ferric, ferrous, titanium or aluminum.
  • the ammonium salts include those in which the ammonium cation has the formula NR 4 R 5 R 6 R 7 wherein each of R 4 , R 5 , R 6 and R 7 are independently hydrogen, hydroxy, (C I -C 4 )alkoxy, (C 1 -C 20 )alkyl, (C 3 -C 8 )alkenyl, (C3-C8)alkynyl, (C 2 -C 8 )hydroxyalkyl, alkoxyalkyl containing a total of 2 to 8 carbon atoms, (C 2 -C 6 )aminoalkyl, (C Z -C 6 )haloalkyl, amino, (C 1 -C 4 )alkyl- or di(C 1 -C 4 )alkylamino, substituted or unsubstituted phenyl, substituted or unsubstituted phenylalkyl, having up to four carbon atoms in the alkyl moiety, or any two of R
  • R 4 , R 5 , R 6 or R 7 substituent in the ammonium group is a substituted phenyl or substituted phenylalkyl
  • the substituents on the phenyl and phenalkyl will generally be selected from halo, (C 1 -C 8 )alkyl, (C I -C 4 )alkoxy, hydroxy, nitro, trifluoromethyl, cyano, amino and (C I -C 4 )alkylthio.
  • Such substituted phenyl groups preferably have up to two such substituents.
  • ammonium cations include ammonium, dimethylammonium, 2-ethylhexyl- ammonium, bis(2-hydroxyethyl)ammonium, tris(2-hydroxyethyl)ammonium, dicyclohexylammonium, t-octylammonium, 2-hydroxyethylammonium, morpholinium, piperidinium, 2-phenethylammonium, 2-methylbenzylammonium, n-hexylammonium, triethylammonium, trimethylammonium, tri(n-butyl)-ammonium, methoxyethylammonium, diisopropylammonium, pyridinium, dialkylammonium, pyrazolium, propargylammonium, dimethylhydrazinium, octadecylammonium, 4-dichlorophenylammonium, 4-nitro- benzylammonium, benzyl
  • the acid addition salts are those in which the anion is an agronomically acceptable anion such as hydrochloride, hydrobromide, sulfate, nitrate, perchlorate, acetate, oxalate and the like.
  • the compounds of the present invention and their precursors can, for example, be made by a process schematically depicted as follows: where X , Y , n, R 1 , R 2 and R 3 are as defined above for Formula I.
  • an omega-chloro-alkanone ethylene ketal having the Formula II such as 5-chloro-2-pentanone ethylene ketal or 6-chloro-3-hexanone ethylene ketal is converted at a temperature below about 100°C and preferably below about 70°C to the corresponding Grignard reagent having the Formula III by procedures well known to those skilled in the art.
  • Step 2 the Grignard reagent from Step 1 is reacted with a suitably substituted benzaldehyde of Formula IV at a temperature of from about -50°C to about 50°C and preferably from about -5°C to about 10°C in a suitable ethereal solvent such as diethyl ether or tetrahydrofuran (THF), preferably THF, to afford the alcohol of Formula V.
  • a suitable ethereal solvent such as diethyl ether or tetrahydrofuran (THF), preferably THF
  • Step 3 Method A, the alcohol of Formula V is subjected to a Jones oxidation (alcohol from Step 2 plus CrO 3 in water containing concentrated sulfuric acid) to afford a I-aryl-1,5-alkanedione of Formula VI.
  • Step 3 where chromium reagents cannot be used, the alcohol of Formula V is treated with manganese dioxide in a halogenated hydrocarbon solvent such as dichloromethane, dichloroethane, chloroform or chlorobenzene, preferably dichloromethane, to afford a ketone of Formula VII.
  • a halogenated hydrocarbon solvent such as dichloromethane, dichloroethane, chloroform or chlorobenzene, preferably dichloromethane
  • Step 4 the 1-aryl-1,5-alkanedione of Formula VI or the ketone of Formula VII is treated with excess hydroxylamine hydrochloride at a temperature of from about 50°C to about 100°C, preferably from about 70°C to about 80°C in a polar solvent such as acetonitrile, methanol, ethanol or dimethylformamide, preferably acetonitrile, to afford a 6-aryl-2-alkylpyridine of Formula VIII.
  • a polar solvent such as acetonitrile, methanol, ethanol or dimethylformamide, preferably acetonitrile
  • hydroxylamine hydrochloride it is meant generally from about 1.5 equivalents to about 5 equivalents, preferably from about 1.5 equivalents to about 2 equivalents, of hydroxylamine hydrochloride per equivalent of the 1-aryl-1,5-alkane- dione of Formula VI or the ketone of Formula VII.
  • Step 5 the 6-aryl-2-alkylpyridine of Formula VIII is treated with selenium dioxide in a suitable ethereal solvent such as tetrahydrofuran (THF) or 1,4-dioxane, preferably 1,4-dioxane to afford the compound of Formula IX.
  • a suitable ethereal solvent such as tetrahydrofuran (THF) or 1,4-dioxane, preferably 1,4-dioxane to afford the compound of Formula IX.
  • Step 6 Method A, the compound of Formula IX is reacted with the thiosemicarbazide of Formula X in a suitable solvent such as alcohols, preferably ethanol, to afford the 6-aryl-pyridine thiosemicarbazones of Formula I.
  • a suitable solvent such as alcohols, preferably ethanol
  • Step 6, Method B the compound of Formula IX is reacted with a methyl hydrazinecarbodithioate of Formula XI in a suitable solvent such as alcohols, preferably isopropyl alcohol, to afford the compound of Formula XII.
  • a suitable solvent such as alcohols, preferably isopropyl alcohol
  • the compound of Formula XII is then reacted with the amine of Formula XIII in a suitable solvent, such as alcohols, preferably methanol, to afford the 6-aryl-pyridine thiosemicarbazones of Formula I.
  • Substantially equimolar amounts of reactants are preferably used in Steps 1 through 6 except Step 4 where an excess of hydroxylamine hydrochloride is employed, although higher or lower amounts can be used if desired.
  • the above process is carried out at about atmospheric pressure, although higher or lower pressures can be used if desired.
  • the agronomically acceptable salts of the thiosemicarbazones of Formula I which are embraced by the invention can be prepared by reacting a metal hydroxide, a metal hydride or an amine or ammonium salt, such as a halide, hydroxide or alkoxide with a compound of Formula I having one or more hydroxy or carboxy groups or reacting a quaternary ammonium salt, such as chloride, bromide, nitrate or the like with a metal salt of a compound of Formula I in a suitable solvent.
  • a metal hydroxide, a metal hydride or an amine or ammonium salt such as a halide, hydroxide or alkoxide
  • a quaternary ammonium salt such as chloride, bromide, nitrate or the like
  • useful solvents include water; ethers such as glyme and the like; dioxane; tetrahydrofuran; alcohols such as methanol, ethanol, isopropanol and the like.
  • useful solvents include nonhydroxylic solvents, for example, ethers such as dioxane, glyme, diethylether and the like; tetrahydrofuran; hydrocarbons such as toluene, xylene, hexane, pentane, heptane, octane and the like; dimethylformamide, and the like.
  • useful solvents include alcohols, such as methanol or ethanol; hydrocarbons, such as toluene, xylene, hexane and the like; tetrahydrofuran; glyme; dioxane; or water.
  • useful solvents include water; alcohols, such as methanol or ethanol; glyme; tetrahydrofuran; or the like.
  • an additional base such as potassium or sodium hydroxide, hydride, or alkoxide is generally used.
  • solvent will depend on the relative solubilities of the starting materials and the resultant salts, and slurries rather than solutions of certain reagents may be used to obtain the salts. Generally, equivalent amounts of the starting reagents are used and the salt-forming reaction is carried out at about 0°C to about 100°C, preferably at about room temperature.
  • the acid addition salts of the invention can be prepared by reacting hydrochloric, hydrobromic, sulfuric, nitric, phosphoric, acetic, propionic, benzoic or other suitable acid with a compound of Formula I having a basic functional group in a suitable solvent.
  • suitable solvents include water, alcohols, ethers, esters, ketones, haloalkanes and the like. The particular choice of solvent will depend on the relative solubilities of the starting materials and the resulting salts and slurries rather than solutions of certain reagents may be used to obtain the salts. Generally, equivalent molar amounts of starting materials are used and the salt-forming reaction is carried out at from about -10°C to about 100°C, preferably at about room temperature.
  • Methyl hydrazinecarbodithioate (5 g) and pyrrolidine (3 g) were dissolved in 50 ml methanol and heated to reflux for 5 hours. After cooling the solid, pyrrolidin-1-yl-thiosemicarbazide was filtered, washed with methanol and air dried. m.p. 177-178°C.
  • the crude ketal-alcohol was dissolved in 200 ml of acetone, cooled to about 5°C and treated with Jones reagent (30 ml). After the addition was complete, the heterogenous mixture was allowed to stand at room temperature for 1.5 hours. The acetone layer was decanted and the residue was extracted with ether. The combined organic extracts were washed with several portions of dilute ammonium hydroxide and then were dried. Evaporation of the solvents afforded 15 g of crude 1-aryl-1,5-hexanedione.
  • the crude diketone was dissolved in 120 ml of acetonitrile and treated with hydroxylamine hydrochloride (0.06 mol, 4.2 g) and heated at 70-80°C for 16 hours.
  • 6-(2-chlorophenyl)-2-formylpyridine-4-(pyrrolidin-1-yl)-thiosemicarbazone was obtained by filtration.
  • the crude thiosemicarbazone was washed with cool ether/methanol and air dried to afford 0.5 g 6-(2-chlorophenyl)-2-formyl- pyridine-4-(pyrrolidin-l-yl)-thiosemicarbazone. m.p. 187-188°C.
  • 6-(2-methylphenyl)-2-methylpyridine was prepared substantially according to the procedures of Example 1 for preparing 6-(2-chlorophenyl)-2-methylpyridine except 2-methylbenzaldehyde was used to afford 6-(2-methylphenyl)-2-methylpyridine.
  • 6-(2-methylphenyl)-2-methylpyridine was dissolved in 180 ml 1,4-dioxane, 1.4 g of selenium dioxide (Aldrich Gold Label) was added and the mixture refluxed for 36 hours. The solids were removed by filtration. Ether was added and the organic extracts washed five times with 100 ml water. After drying over magnesium sulfate and evaporation, 6-(2-methylphenyl)-2-pyridinecarboxaldehyde was afforded as a pale yellow oil (1.4 g).
  • 6-(2-methylphenyl)-pyridinecarboxaldehyde was dissolved in 5 ml absolute ethanol and treated with 0.35 g of pyrrolidin-1-yl-thiosemicarbazide. After 3 for preparing 6-(2-chlorophenyl)-2-methylpyridine except 2-fluorobenzaldehyde was used to afford 6-(2-fluorophenyl)-2-methylpyridine.
  • 6-(2-fluorophenyl)-2-methylpyridine was dissolved in 250 ml of 1,4-dioxane.
  • Selenium dioxide (2.67 g, Aldrich Gold Label) was added and the mixture was refluxed for 6 days. The solids were removed by filtration and the dioxane was evaporated.
  • the crude 6-(2-fluorophenyl)-2-pyridinecarboxaldehyde was purified by chromatography on silica gel to afford pure 6-(2-fluorophenyl)-2-pyridinecarboxaldehyde.
  • 6-(2-trifluoromethylphenyl)-2-methylpyridine was prepared substantially according to the procedures of Example 1 for preparing 6-(2-chlorophenyl)-2-methylpyridine except 2-trifluoromethylbenzaldehyde was used to afford 6-(2-trifluoromethylphenyl)-2-methylpyridine.
  • the crude 6-(2-methylphenyl)-2-formyl- pyridine-4-(pyrrolidin-1-yl)-thiosemicarbazone was isolated by filtration. The crude solids were washed well with absolute ethanol and dried in air to afford 0.4 g of 6-(2-methylphenyl)-2-formylpyridine-4-(pyrrolidin-l-yl)-thiosemicarbazone. m.p. 172-173°C.
  • 6-(2-bromophenyl)-2-methylpyridine was prepared substantially according to the procedures of Example 1 for preparing 6-(2-chlorophenyl)-2-methylpyridine except 2-bromobenzaldehyde was used to afford 6-(2-bromophenyl)-2-methylpyridine.
  • 6-(2-bromophenyl)-2-methylpyridine (3.5 g) was dissolved in 150 ml 1,4-dioxane.
  • Selenium dioxide Aldrich, Gold Label, 2.0 g was added and the mixture was refluxed for a total of 50 hours. The solids were removed by filtration and the mixture was diluted with ether. The solution was washed several times with water, dried over magnesium sulfate, filtered and evaporated to afford 2.0 g of crude (6-(2-bromophenyl)-2-pyridinecarboxaldehyde as a yellow semi-solid.
  • 6-(2-trifluoromethylphenyl)-2-pyridinecarboxaldehyde was dissolved in 10 ml ethanol and treated with 0.35 g of pyrrolidin-1-yl-thiosemicarbazide. After stirring the mixture at 23°C for 6 hours, 6-(2-trifluoromethylphenyl)-2-formylpyridine-4-(pyrrolidine-1-yl)-thiosemicarbazone was isolated by filtration and purified by washing with ethanol. m.p. 142-146°C.
  • 6-(2,4-dichlorophenyl)-2-methylpyridine was prepared substantially according to the procedures of Example 1 for preparing 6-(2-chlorophenyl)-2-methylpyridine except 2,4-dichlorobenzaldehyde was used to afford 6-(2,4-dichlorophenyl)-2-methylpyridine.
  • 6-(2,4-dichlorophenyl)-2-pyridinecarbox- aldehyde 0.5 g was dissolved in 15 ml of ethanol and treated with 0.29 g of pyrrolidin-1-yl-thiosemicarbazide. After stirring at 23°C for 18 hours, 6-(2,4-dichlorophenyl)-2-formylpyridine-4-(pyrrolidin-1-yl)-thiosemicarbazone was isolated by filtration and purified by washing with methanol. m.p. 155-156°C.
  • 6-(2-chloro-4,5-dioxolanophenyl)-2-pyridine- aldehyde was prepared substantially according to the procedures of Example 1 for preparing 6-(2-chlorophenyl)-2-pyridinealdehyde except 2-chloro-4,5-dioxolanobenzaldehyde was used to afford 6-(2-chloro-4,5-dioxolanophenyl)-2-pyridinecarboxaldehyde.
  • the compounds of the present invention exhibit insecticidal activity and are selective against larvae of the order Lepidoptera.
  • the insecticidal compounds of the invention may be used at a dosage corresponding to from about 10 grams to about 10 kilograms of the active substance per hectare and from about 100 grams to about 5 kilograms per hectare of the active substance is preferred.
  • the exact amount of dosage for a given situation can be routinely determined and depends on a variety of factors, for example, the substance used, the kind of insect, the formulation used, the state of the crop infested with the insect and the prevailing weather conditions.
  • the term "insecticidal" as employed in the specification and claims of this application is to be construed as any means which adversely affects the existence or growth of the target insects.
  • control and “combat”, used herein, we mean an "insecticidal” action or the protection, for-example of plants, from insect damage.
  • insecticidally effective amount is meant that dosage of active substance sufficient to exert insect "control”.
  • compositions or formulations can be utilized in the form of compositions or formulations.
  • preparation of compositions and formulations can be found in the American Chemical Society publication “Pesticidal Formulation Research", (1969) Advances in Chemistry Series No. 86, written by Wade Van Valkenburg; and the Marcel Dekker, Inc., publication “Pesticide Formulations”, (1973), edited by Wade Van Valkenburg.
  • the active substance or substances are mixed with conventional inert agronomically acceptable (i.e., plant compatible and/or pesticidally inert) diluents or extenders such as solid carrier material or liquid carrier material, of the type usable in conventional compositions or formulations.
  • agronomically acceptable carrier any substance which can be used to dissolve, disperse or diffuse the active ingredient in the composition without impairing the active ingredient's effectiveness and which by itself has no significant detrimental effect on the soil, equipment, desirable plants or agronomic environment.
  • conventional adjuvants such as surfactants, stabilizers, antifoam agents and antidrift agents may also be added.
  • compositions and formulations according to the invention are aqueous solutions and dispersions, oily solutions and oil dispersions, pastes dusting powders, wettable powders, emulsifiable concentrates, flowables, granules, baits, invert emulsions, aerosol compositions and fumigating candles.
  • Wettable powders, pastes, flowables and emulsifiable concentrates are concentrated preparations which are diluted with water before or during use.
  • Baits are preparations generally comprising a food or other substance attractive to the target pest, that includes at least one lethal or non-lethal toxicant.
  • Lethal toxicants kill the pest upon ingesting the bait while non-lethal toxicants change the behavior, feeding habits and physiology of the pest for the purpose of control.
  • the invert emulsions are mainly used for air application, where large areas are treated with a comparatively small amount of preparation.
  • the invert emulsion may be prepared in the spraying apparatus shortly before, or even during, the spraying operation by emulsifying water in an oil solution or an oil dispersion of the active substance.
  • compositions and formulations are prepared in a known manner, for instance by extending the active compounds with conventional dispersible liquid diluent carriers and/or dispersible solid carriers optionally with the use of carrier vehicle assistants, e.g., conventional surface-active agents, including emulsifying agents and/or dispersing agents, whereby, for example, in the case where water is used as diluent, organic solvents may be added as auxiliary solvents.
  • carrier vehicle assistants e.g., conventional surface-active agents, including emulsifying agents and/or dispersing agents
  • aerosol propellants which are gaseous at normal temperatures and pressures, such as halogenated hydrocarbons, e.g., dichlorodifluoromethane and trifluorochloromethane, as well as butane, propane, nitrogen and carbon dioxide; inert dispersible liquid diluent carriers, including inert organic solvents, such as aromatic hydrocarbons (e.g., benzene, toluene, xylene, alkyl naphthalenes, etc.), halogenated, especially chlorinated, aromatic hydrocarbons (e.g., chlorobenzenes, etc.), cycloalkanes (e.g., cyclohexane, etc.), paraffins (e.g., petroleum or mineral oil fractions), chlorinated aliphatic hydrocarbons (e.g., methylene chloride, chloroethylenes, etc.), vegetable oils (e.g.
  • halogenated hydrocarbons e.g., dich
  • emulsifying agents such as cationic and/or nonionic and/or anionic emulsifying agents (e.g., polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolysates, etc., and especially alkyl arylpolyglycol ethers, magnesium stearate, sodium oleate, etc.); and/or dispersing agents, such as lignin, sulfite waste liquors, methyl cellulose, etc.
  • emulsifying agents such as cationic and/or nonionic and/or anionic emulsifying agents (e.g., polyethylene oxide esters of fatty acids, polyethylene oxide ethers of fatty alcohols, alkyl sulfates, alkyl sulfonates, aryl sulfonates, albumin hydrolysates, etc.
  • Adhesives such as carboxymethylcellulose and natural and synthetic polymers in the form of powders, granules or latices, such as gum arabic, polyvinyl alcohol and polyvinyl acetate, can be used in the formulations.
  • colorants in compositions and formulations containing compounds of the present invention such as inorganic pigments, for example, iron oxide, titanium oxide and Prussian Blue, and organic dyestuffs, such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs, and trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • inorganic pigments for example, iron oxide, titanium oxide and Prussian Blue
  • organic dyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthalocyanine dyestuffs
  • trace nutrients such as salts of iron, manganese, boron, copper, cobalt, molybdenum and zinc.
  • the active compounds of the present invention may be employed alone or in the form of mixtures with one another and/or with such solid and/or liquid dispersible carrier vehicles and/or with other known compatible active agents, especially plant protection agents, such as other insecticides, arthropodicides, nematicides, fungicides, bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, synergists, etc., if desired, or in the form of particular dosage preparations for specific application made therefrom, such as solutions, emulsions, suspensions, powders, pastes, and granules which are thus ready for use.
  • plant protection agents such as other insecticides, arthropodicides, nematicides, fungicides, bactericides, rodenticides, herbicides, fertilizers, growth-regulating agents, synergists, etc.
  • carrier composition mixtures in which the active compound is present in an amount substantially between about 0.1% and 99% by weight, and preferably between about 1% and 75% by weight, of the mixture.
  • Carrier composition mixtures suitable for direct application or field application generally contemplate those in which the active compound is used in an amount substantially between about 0.0001% and 5%, preferably between about 0.001% and 3%, by weight of the mixture.
  • the present invention contemplates overall formulations and compositions which comprise mixtures of a conventional dispersible carrier such as (1) a dispersible inert finely divided carrier solid, and/or (2) a dispersible carrier liquid such as an inert organic solvent and/or water, preferably including a surface-active effective amount of a carrier vehicle assistant (e.g., a surface-active agent, such as an emulsifying agent and/or a dispersing agent), and an amount of the active compound generally, between about 0.0001% and about 99% by weight of the composition, preferably between about 0.001% and about 90% by weight of the composition, and more preferably between about 0.01% and about 75% by weight of the composition, which is effective for the purpose in question.
  • a carrier vehicle assistant e.g., a surface-active agent, such as an emulsifying agent and/or a dispersing agent
  • an amount of the active compound generally, between about 0.0001% and about 99% by weight of the composition, preferably between about 0.001% and about 90%
  • the active compounds can be applied as sprays by methods commonly employed, such as conventional high- gallonage hydraulic sprays, low gallonage sprays, ultra-low-volume sprays, airblast spray, aerial sprays, and dusts. If low volume applications are desired, a solution of the compound is usually used. In ultra-low-volume applications, a liquid composition containing the active compound is usually applied as a spray (e.g., mist) by means of atomizing equipment in finely divided form (average particle size of from about 50 to about 100 microns or less) using airplane crop spraying techniques. Typically only a few liters per hectare are needed and often amounts up to about 15 to 1000 g/hectare, preferably about 40 to 600 g/hectare are sufficient. With ultra-low-volume, it is possible to use highly concentrated liquid compositions with said liquid carrier vehicles containing from about 20 to about 95% by weight of the active compound.
  • the present invention contemplates methods of killing, combatting or controlling insects, which comprises contacting insects with a correspondingly combative or toxic amount (i.e., an insecticidally effective amount) of at least one active compound of the invention alone or together with a carrier vehicle (composition or formulation) as noted above.
  • a correspondingly combative or toxic amount i.e., an insecticidally effective amount
  • the term "contacting" as employed in the specification and claims of this application is to be construed as applying to at least one of (a) such insects and (b) the corresponding habitat thereof (i.e., the locus to be protected, for example, to a growing crop or to an area where a crop is to be grown) the active compound of this invention alone or as a constituent of a composition or formulation.
  • the instant formulations or compositions are applied in the usual manner, for instance by spraying, atomizing, vaporizing, scattering, dusting, watering, squirting, sprinkling, pouring, fumigating, dry dressing, moist dressing, wet dressing, slurry dressing, encrusting and the like.
  • concentration of the particular active compound utilized in admixture with the carrier vehicle will depend upon such factors as the type of equipment employed, method of application, area to be treated, types of insects to be controlled and degree of infestation. Therefore, in special cases it is possible to go above or below the aforementioned concentration ranges.
  • Granular preparations are produced for example, by taking up the active substance in a solvent and by using the resulting solution, as the case may be in the presence of a binder, to impregnate a granular carrier material, such as porous granules (for example, pumice and attaclay), or chopped tobacco stems or the like.
  • a granular carrier material such as porous granules (for example, pumice and attaclay), or chopped tobacco stems or the like.
  • a granular preparation (frequently termed a "pellet") may alternatively be produced by compressing the active substance together with powdered minerals in the presence of lubricants and binders and by disintegrating and straining the composite to the desired grain size.
  • Dusts are obtaintable by intimately mixing the active substance with an inert solid carrier material in a concentration of from about 1 to about 50% by weight.
  • solid carrier materials are talc, kaolin, pipe clay, diatomaceous earth, dolomite, gypsum, chalk, bentonite, attapulgite and colloidal Si0 2 or mixtures of these and similar substances.
  • organic carrier materials such as, for example, ground walnut shells may be used.
  • Wettable powders and flowables are produced by mixing from about 10 to about 99 parts by weight of a solid inert carrier such, for example, as the aforementioned carrier materials with from about 1 to about 80 parts by weight of the active substance optionally dissolved in a volatile solvent such as acetone, from about 1 to about 5 parts by weight of a dispersing agent such, for example, as the lignosulfonates or alkylnaphthalene sulfonates known for this purpose and preferably also from about 0.5 to about 5 parts by weight of a wetting agent, such as fatty alcohol sulfates, or alkylarylsulfonates of fatty acid condensation products.
  • a liquid inert carrier such as water is also included.
  • emulsifiable concentrates the active compound is dissolved or finely divided in a suitable solvent which preferably is poorly miscible with water, an emulsifier being added to the resulting solution.
  • suitable solvents are xylene, toluene, high-boiling aromatic petroleum distillates, for example solvent naphtha, distilled tar oil and mixtures of these liquids.
  • suitable emulsifiers are alkylphenoxypolyglycol ethers, polyoxyethylene sorbitan esters of fatty acids or polyoxyethylene sorbitol esters of fatty acids.
  • concentration of the active compound in these emulsifiable concentrates is not restricted within narrow limits and may vary between about 2% and about 50% by weight depending upon toxicant solubility.
  • a suitable liquid highly concentrated primary composition other than an emulsifiable concentrate is a solution of the active substance in a liquid which is readily miscible with water, for example, acetone, to which solution a dispersant and, as the case may be, a wetting agent are added. When such a primary composition is diluted with water shortly before or during the spraying operation an aqueous dispersion of the active substance is obtained.
  • An aerosol preparation according to the invention is obtained in the usual manner by incorporating the active substance or a solution thereof in a suitable solvent in a volatile liquid suitable for use as a propellant such, for example, as a mixture of chlorine and fluorine derivatives of methane and ethane.
  • Fumigating candles or fumigating powders i.e., preparations which when burning are capable of emitting a pesticidal smoke, are obtained by taking up the active substance in a combustible mixture which may, for example, comprise a sugar or a wood, preferably in the ground form, as a fuel, a substance to sustain combustion such, for example, as ammonium nitrate or potassium chlorate, and furthermore a substance for retarding combustion, for example kaolin, bentonite and/or colloidal silicic acid.
  • a combustible mixture which may, for example, comprise a sugar or a wood, preferably in the ground form, as a fuel, a substance to sustain combustion such, for example, as ammonium nitrate or potassium chlorate, and furthermore a substance for retarding combustion, for example kaolin, bentonite and/or colloidal silicic acid.
  • a bait preparation comprises a food or other substance attractive to pests, a carrier, the toxicant and may optionally include other substances commonly used in preparations of this kind, such as, a preservative to inhibit bacterial and fungal growth, a waterproofing agent to prevent disintegration under wet conditions and dyes or colorants as described above.
  • the preparations according to the invention may also contain other substances commonly used in preparations of this kind.
  • a lubricant such as calcium stearate or magnesium stearate
  • a lubricant such as calcium stearate or magnesium stearate
  • a lubricant such as calcium stearate or magnesium stearate
  • a wettable powder or to a mixture to be granulated.
  • adheresives such as polyvinylalcohol cellulose derivatives or other colloidal materials, such as casin, to improve the adherence of this pesticide to the surface to be protected.
  • compositions and formulations including the compounds of the present invention are set forth below as Examples C through K by way of illustration but not limitation.
  • Toxicant is dissolved in excess acetone and the mixture is impregnated onto the talc. The acetone is then permitted to evaporate.
  • the toxicant optionally dissolved in a volatile solvent, is absorbed onto the Barden clay and HiSil carriers.
  • the Duponal and Reax are then added and the entire dry mixture blended until homogeneous.
  • the composition is then micronized to a fine particle size.
  • Preparation The components are mixed and packaged under pressure in a suitable container equipped with a release spray valve.
  • Toxicant, wood dust, and starch are blended together and then molded into a candle using a small amount of water to activate the starch.
  • Preparation The corn oil and corn syrup are added to the wheat bran with adequate mixing.
  • the toxicant and Kathon are premixed with excess acetone and this solution is added to the wheat bran base with continued mixing.
  • the acetone is then permitted to evaporate.
  • the bait composition is formed into 1/4" diameter by 3/8" long pellets using a suitable die and press apparatus.
  • the toxicant is absorbed onto the HiSil carrier.
  • the Duponal and Reax are then added and the entire dry mixture blended until homogeneous.
  • the composition is then micronized to a fine particle size.
  • the resulting powder is suspended in water and the Kelzan added.
  • compositions and formulations according to the present invention may also include known pesticidal compounds. This expands the spectrum of activity of the preparations and may give rise to synergism.
  • the following known insecticidal, fungicidal and acaricidal compounds are suitable for use in such a combined preparation.
  • Insecticides such as:
  • Fungicides such as:
  • the compounds of the present invention in part affect the normal development of insects, particularly insects from the order Lepidoptera, by directly and/or indirectly influencing the moulting process.
  • the compounds of the present invention when consumed by larvae, such larvae undergo a premature, lethal metamorphosis. It is believed the compounds of the present invention exhibit anti-juvenile hormone activity. This activity is believed to be unique and helps to distinguish compounds of the present invention from known compounds.
  • the compounds of the present invention are particularly suitable for controlling plant destructive insects in crops of cultivated plants, such as, but not limited to, cotton, vegetables, corn and other cereals and the like; forestry, such as, but not limited to, birch, spruce, pine, fir and the like; and ornamental plants, flowers and trees.
  • Compounds of the present invention are also particularly suitable for controlling insects destructive to stored commodities such as seeds and the like; fruit crops, such as, but not limited to fruit and/or citrus trees, raspberry bushes and the like.
  • Larvae of the tobacco budworm (Heliothis viriscens F.) were raised from the egg stage on commercially available black cutworm diet (from Bioserv, U.S.A.) at 26°C, 16 hours of light, 8 hours of darkness.
  • Newly ecdysed penultimate instar budworms (4th instar) were fed the black cutworm diet into which the experimental compound had been incorporated by admixing a solution of the compound in 0.5 ml dimethyl sulfoxide/acetone (1:1) into 100 ml of the diet while it was fluid (65°C).
  • the test larvae were kept in individual containers.
  • the budworms were observed after 10 days for morphological outcome, especially precocious pupal characteristics.
  • the results of the initial insecticidal evaluations are given in Table II.
  • the evaluations are based on a scale of 0-100 in which 0 equals no activity and 100 equals total premature metamorphosis. Such premature metamorphosis will result in death.
  • a process of the invention for improving the commercial value and/or profitability of vendible crops from plants whose growth is affected or likely to be affected by insects comprises (1) charging to a container, fumigation device or mechanical dissemination device an insecticidal composition of the invention as hereinbefore described (2) using the container, fumigator or mechanical dissemination device to apply the insecticidal composition, in the form of granules, dust, smoke, vapour or surfactant-containing liquid preparation to growing plants or to a growth medium where the plants are growing or are to be grown, or to the insects themselves, (3) controlling the dose of the active ingredient during this application step so that the rate of application of active insecticidal compound is sufficient to combat the insects but is insufficient to cause an unacceptably adverse effect on the crop plants growing or to be grown in the treated area.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Agronomy & Crop Science (AREA)
  • Pest Control & Pesticides (AREA)
  • Plant Pathology (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Dentistry (AREA)
  • General Health & Medical Sciences (AREA)
  • Wood Science & Technology (AREA)
  • Zoology (AREA)
  • Environmental Sciences (AREA)
  • Pyridine Compounds (AREA)
  • Plural Heterocyclic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
EP87303374A 1986-04-25 1987-04-16 6-Arylpyridinthiosemicarbazone mit Wirksamkeit als Insektizide Withdrawn EP0243101A3 (de)

Applications Claiming Priority (2)

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US06/856,629 US4696938A (en) 1986-04-25 1986-04-25 Insecticidal 6-aryl-pyridine thiosemicarbazones
US856629 1986-04-25

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EP0243101A2 true EP0243101A2 (de) 1987-10-28
EP0243101A3 EP0243101A3 (de) 1989-08-02

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US5861526A (en) * 1996-11-07 1999-01-19 Bayer Corporation Process for reducing dithiocarbazinate buildup in the preparation of methyl dithiocarbazinate
US6025514A (en) * 1996-11-07 2000-02-15 Bayer Corporation Process for preparing methyl dithiocarbazinate by reacting methyl bromide with the reaction product of carbon disulfide, hydrazine and an adjunct base
CA2218853C (en) * 1996-11-07 2008-04-22 Bayer Corporation A process for preparing methyl dithiocarbazinate by reacting methyl bromide with the reaction product of carbon disulfide, hydrazine and an adjunct base
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Publication number Priority date Publication date Assignee Title
EP2461687A4 (de) * 2009-08-07 2013-03-20 Dow Agrosciences Llc Pestizidzusammensetzungen
US8680269B2 (en) 2009-08-07 2014-03-25 Dow Agrosciences, Llc. Pesticidal compositions
AU2010279373B2 (en) * 2009-08-07 2014-05-01 Dow Agrosciences Llc Pesticidal compositions
US9179681B2 (en) 2009-08-07 2015-11-10 Dow Agrosciences Llc Pesticidal compositions

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JPS62258360A (ja) 1987-11-10
CA1310645C (en) 1992-11-24
KR870010002A (ko) 1987-11-30
US4696938A (en) 1987-09-29
KR950002155B1 (ko) 1995-03-14
EP0243101A3 (de) 1989-08-02

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